Journal of Materials Science

, Volume 49, Issue 7, pp 2853–2863 | Cite as

Establishment of a novel surface-imprinting system for melamine recognition and mechanism of template–matrix interactions

  • Xiuzhu Xu
  • Shuixia Chen
  • Linzhou Zhuang
  • Chunhao Zheng
  • Yingzhu Wu


A surface molecular-imprinting system was developed on polypropylene (PP) fiber for melamine (Mel) as an N-containing template. In this article, acrylic acid was introduced onto the surface of PP for template binding. Subsequently, binding sites on PP were stabilized by crosslinking with ethylene glycol diglycidyl ether in the presence of Mel. The imprinted fiber (MIF-Mel) prepared with the optimal 15 % crosslinking density showed best-imprinting effect, with an imprinting factor of 2.18 respect to nonimprinted fiber, and a relative selectivity coefficient k′ of 10.40 for Mel with respect to its structural analog 2,4-dinitroaniline. MIF-Mel showed higher affinity to Mel with the maximum adsorption capacity of 15.5 mg g−1, while that on nonimprinted fiber was only 6.9 mg g−1. Its adsorption isotherm was well described using Langmuir model. Kinetic studies showed a rapid-binding interaction and high affinity of the MIF-Mel for its template, with a 2.5 times higher in binding amount and 4.7 times faster in binding speed than those of granular molecular-imprinting polymer with the same chemical structure. High degree of fitness with pseudo-second-order model revealed chemisorption was the rate-controlling step in the template-binding process. Basic theory of matrix–template interaction in this imprinting system was clarified to be dominated by electrostatic force synergized by hydrogen bonding between deprotonated carboxyl groups and protonated N atom in the template. It suggests that extension of this novel approach or theory to other imprinting system involving nitrogenous templates is very likely.


Adsorption Capacity Melamine Crosslinking Density Selectivity Coefficient Imprint Cavity 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.



The authors gratefully acknowledge the financial support provided by the National Natural Science Foundation of China (Grant No. 51173211), Science and Technology Project of Guangdong Province (2011B090400030), Science and Technology Project of Zhuhai (2010B050102024).

Supplementary material

10853_2013_7991_MOESM1_ESM.doc (154 kb)
Supplementary material 1 (DOC 154 kb)


  1. 1.
    Sibrian-Vazquez M, Spivak DA (2004) Molecular imprinting made easy. J Am Chem Soc 126:7827–7833CrossRefGoogle Scholar
  2. 2.
    Ansell R (2005) Molecularly imprinted polymers for the enantioseparation of chiral drugs. Adv Drug Deliv Rev 57:1809–1835CrossRefGoogle Scholar
  3. 3.
    Greene NT, Morgan SL, Shimizu KD (2004) Molecularly imprinted polymer sensor arrays. Chem Commun 10:1172–1173CrossRefGoogle Scholar
  4. 4.
    Ramström O, Mosbach K (1999) Synthesis and catalysis by molecularly imprinted materials. Curr Opin Chem Biol 3:759–764CrossRefGoogle Scholar
  5. 5.
    Wulff G (2002) Enzyme-like catalysis by molecularly imprinted polymers. Chem Rev 102:1–27CrossRefGoogle Scholar
  6. 6.
    Balamurugan K, Gokulakrishnan K, Prakasam T (2011) Preparation and evaluation of molecularly imprinted polymer liquid chromatography column for the separation of ephedrine enantiomers. Arab J Chem 2:77Google Scholar
  7. 7.
    Yang H–H, Zhang S-Q, Yang W, Chen X-L, Zhuang Z-X, Xu J-G, Wang X-R (2004) Molecularly imprinted sol–gel nanotubes membrane for biochemical separations. J Am Chem Soc 126:4054–4055CrossRefGoogle Scholar
  8. 8.
    Cunliffe D, Kirby A, Alexander C (2005) Molecularly imprinted drug delivery systems. Adv Drug Deliv Rev 57:1836–1853Google Scholar
  9. 9.
    Wei X, Li X, Husson SM (2005) Surface molecular imprinting by atom transfer radical polymerization. Biomacromolecules 6:1113–1121CrossRefGoogle Scholar
  10. 10.
    Kempe H, Kempe M (2004) Novel method for the synthesis of molecularly imprinted polymer bead libraries. Macromol Rapid Commun 25:315–320CrossRefGoogle Scholar
  11. 11.
    Ye L, Mosbach K (2001) Molecularly imprinted microspheres as antibody binding mimics. React Funct Polym 48:149–157CrossRefGoogle Scholar
  12. 12.
    Hirayama K, Sakai Y, Kameoka K (2001) Synthesis of polymer particles with specific lysozyme recognition sites by a molecular imprinting technique. J Appl Polym Sci 81:3378–3387CrossRefGoogle Scholar
  13. 13.
    Strikovsky A, Hradil J, Wulff G (2003) Catalytically active, molecularly imprinted polymers in bead form. React Funct Polym 54:49–61CrossRefGoogle Scholar
  14. 14.
    Lepinay S, Kham K, Millot MC, Carbonnier B (2012) In-situ polymerized molecularly imprinted polymeric thin films used as sensing layers in surface plasmon resonance sensors: mini-review focused on 2010-2011. Chem Pap 66:340–351CrossRefGoogle Scholar
  15. 15.
    Das K, Penelle J, Rotello VM (2003) Selective picomolar detection of hexachlorobenzene in water using a quartz crystal microbalance coated with a molecularly imprinted polymer thin film. Langmuir 19:3921–3925CrossRefGoogle Scholar
  16. 16.
    Huang HC, Lin CI, Joseph AK, Lee YD (1027) Photo-lithographically impregnated and molecularly imprinted polymer thin film for biosensor applications. J Chromatoge A 2004:263–268Google Scholar
  17. 17.
    Duffy DJ, Das K, Hsu SL, Penelle J, Rotello VM, Stidham HD (2002) Binding efficiency and transport properties of molecularly imprinted polymer thin films. J Am Chem Soc 124:8290–8296CrossRefGoogle Scholar
  18. 18.
    Gauczinski J, Liu Z, Zhang X, Schönhoff M (2012) Surface molecular imprinting in layer-by-layer films on silica particles. Langmuir 28:4267–4273CrossRefGoogle Scholar
  19. 19.
    Yan W, Gao R, Zhang Z, Wang Q, Jiang CV, Yan C (2003) Capillary electrochromatographic separation of ionizable compounds with a molecular imprinted monolithic cationic exchange column. J Sep Sci 26:555–561CrossRefGoogle Scholar
  20. 20.
    Schweitz L, Andersson LI, Nilsson S (1997) Capillary electrochromatography with molecular imprint-based selectivity for enantiomer separation of local anaesthetics. J Chromatoge A 792:401–409CrossRefGoogle Scholar
  21. 21.
    Che A-F, Wan L-S, Ling J, Liu Z-M, Xu Z-K (2009) Recognition mechanism of theophylline-imprinted polymers: two-dimensional infrared analysis and density functional theory study. J Phys Chem B 113:7053–7058CrossRefGoogle Scholar
  22. 22.
    Özacar M, Şengil İA (2003) Adsorption of reactive dyes on calcined alunite from aqueous solutions. J Hazard Mater 98:211–224CrossRefGoogle Scholar
  23. 23.
    Skorik Y (2012) Carboxyethylated polyaminostyrene for selective copper removal. Polym Bull 68:1065–1078CrossRefGoogle Scholar
  24. 24.
    Vorderbruggen MA, Wu K, Breneman CM (1996) Use of cationic aerosol photopolymerization to form silicone microbeads in the presence of molecular templates. Chem Mater 8:1106–1111CrossRefGoogle Scholar
  25. 25.
    Ran D, Wang Y, Jia X, Nie C (2012) Bovine serum albumin recognition via thermosensitive molecular imprinted macroporous hydrogels prepared at two different temperatures. Anal Chim Acta 723:45–53CrossRefGoogle Scholar
  26. 26.
    Rostamizadeh K, Vahedpour M, Bozorgi S (2012) Synthesis, characterization and evaluation of computationally designed nanoparticles of molecular imprinted polymers as drug delivery systems. Int J Pharm 424:67–75CrossRefGoogle Scholar
  27. 27.
    Ersöz A, Say R, Denizli A (2004) Ni(II) ion-imprinted solid-phase extraction and preconcentration in aqueous solutions by packed-bed columns. Anal Chim Acta 502:91–97CrossRefGoogle Scholar
  28. 28.
    Cao Q, Zhao H, Zeng L, Wang J, Wang R, Qiu X, He Y (2009) Electrochemical determination of melamine using oligonucleotides modified gold electrodes. Talanta 80:484–488CrossRefGoogle Scholar
  29. 29.
    Nityanandi D, Subbhuraam CV (2009) Kinetics and thermodynamic of adsorption of chromium(VI) from aqueous solution using puresorbe. J Hazard Mater 170:876–882CrossRefGoogle Scholar
  30. 30.
    Cheng HC (2004) The influence of cooperativity on the determination of dissociation constants: examination of the Cheng–Prusoff equation, the Scatchard analysis, the Schild analysis and related power equations. Pharmacol Res 50:21–40CrossRefGoogle Scholar
  31. 31.
    Ying X, Cheng G, Li X (2011) The imprinting induce-fit model of specific rebinding of macromolecularly imprinted polymer microspheres. J Appl Polym Sci 122:1847–1856CrossRefGoogle Scholar
  32. 32.
    Patachia S, Croitoru C (2011) Imprinted poly (vinyl alcohol) as a promising tool for xanthine derivatives separation. J Appl Polym Sci 122:2081–2089CrossRefGoogle Scholar
  33. 33.
    Tseng R-L, Wu F-C, Juang R-S (2010) Characteristics and applications of the Lagergren’s first-order equation for adsorption kinetics. J Taiwan Inst Chem E 41:661–669CrossRefGoogle Scholar
  34. 34.
    Ho YS, McKay G (1999) The sorption of lead(II) ions on peat. Water Res 33:578–584CrossRefGoogle Scholar
  35. 35.
    Ho YS, McKay G (1999) Pseudo-second order model for sorption processes. Process Biochem 34:451–465CrossRefGoogle Scholar
  36. 36.
    Özacar M, Şengil İA, Türkmenler H (2008) Equilibrium and kinetic data, and adsorption mechanism for adsorption of lead onto valonia tannin resin. Chem Eng J 143:32–42CrossRefGoogle Scholar
  37. 37.
    Li T, Chen S, Li H, Li Q, Wu L (2011) Preparation of an ion-imprinted fiber for the selective removal of Cu2+. Langmuir 27:6753–6758CrossRefGoogle Scholar
  38. 38.
    Chiou M-S, Li H-Y (2002) Equilibrium and kinetic modeling of adsorption of reactive dye on cross-linked chitosan beads. J Hazard Mater 93:233–248CrossRefGoogle Scholar
  39. 39.
    Yang H–H, Zhang S-Q, Tan F, Zhuang Z-X, Wang X-R (2005) Surface molecularly imprinted nanowires for biorecognition. J Am Chem Soc 127:1378–1379CrossRefGoogle Scholar
  40. 40.
    Lu C-H, Zhou W-H, Han B, Yang H–H, Chen X, Wang X-R (2007) Surface-imprinted core–shell nanoparticles for sorbent assays. Anal Chem 79:5457–5461CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2014

Authors and Affiliations

  • Xiuzhu Xu
    • 1
  • Shuixia Chen
    • 1
    • 2
  • Linzhou Zhuang
    • 1
  • Chunhao Zheng
    • 1
  • Yingzhu Wu
    • 1
  1. 1.PCFM Lab, School of Chemistry and Chemical EngineeringSun Yat-Sen UniversityGuangzhouPeople’s Republic of China
  2. 2.DSAPM Lab, Materials Science InstituteSun Yat-Sen UniversityGuangzhouPeople’s Republic of China

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